TWI363079B - Flame retardant seal - Google Patents
Flame retardant seal Download PDFInfo
- Publication number
- TWI363079B TWI363079B TW093137114A TW93137114A TWI363079B TW I363079 B TWI363079 B TW I363079B TW 093137114 A TW093137114 A TW 093137114A TW 93137114 A TW93137114 A TW 93137114A TW I363079 B TWI363079 B TW I363079B
- Authority
- TW
- Taiwan
- Prior art keywords
- flame
- sealing material
- flame retardant
- weight
- elastic sheet
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 46
- 239000003566 sealing material Substances 0.000 claims description 45
- 239000006260 foam Substances 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 24
- 150000004692 metal hydroxides Chemical class 0.000 claims description 22
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 21
- 238000005187 foaming Methods 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 18
- 239000004088 foaming agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 240000005373 Panax quinquefolius Species 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- 229930007744 linalool Natural products 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000002904 solvent Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000006261 foam material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000011027 product recovery Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- CMBZEFASPGWDEN-UHFFFAOYSA-N argon;hydrate Chemical compound O.[Ar] CMBZEFASPGWDEN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- JNSHJDXBICHABV-UHFFFAOYSA-N 11-oxatetracyclo[7.5.0.02,7.010,12]tetradeca-1(9),2,4,6,13-pentaene Chemical compound C12C(C=CC=3C4=CC=CC=C4CC13)O2 JNSHJDXBICHABV-UHFFFAOYSA-N 0.000 description 1
- 101100289061 Drosophila melanogaster lili gene Proteins 0.000 description 1
- 238000003811 acetone extraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000012897 dilution medium Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
- C08G18/0857—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic the solvent being a polyol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/12—Hydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
1363079 九、發明說明： 【發明所屬之技術領域】 本發明係關於難燃性密封材。詳而言之，本發明之難 燃性密封材，係具備優異的密封性及難燃性，可使用於高 溫環境氣氛般之嚴酷環境下，且適用於高發熱性之電子= 器與精密機器者。 【先前技術】 订動電話、電視、電腦等之顯示器般的電氣機器，係 配設有液晶顯示部、麥克風部、揚聲器部等的輸出入部。 這些輸出入部，係設於電氣機器框體之向外開口的部位。 因此，例如液晶顯示部的情形，在液晶顯示部的周緣與框 體，間，係配設有密封材，以防止灰塵之入侵、液晶顯示 用背光之漏光，並防止其與框體間之晃動。近年來，以行 動電話為代表之各種電氣機器有高機能化及輕量化的: 求’基於此也要求密封材之小型、薄型化。密封材之材料* 基於就算較薄也能充分發揮密封材的作用，適用者為柔軟 性優異且低硬度之聚氨醋發泡體。又，聚氧賴發泡體由： 材料之劣化(變質)及氣體產生較少，故適用於當 電氣機器框體内之密封材。 ' 具有良好的 ’且形成具 及電子機器 。因此，密 密 有 時 '聚氨酯發泡體構成之密封材，如前述般， 封材特性《然而，該密封材係由有機物構成 高比表面積之薄片狀，當組裝於電氣機器 ，因該等機器作動時產生的熱可能變成高溫 丄 封材仏要求高難燃性。 係使密封材之原料中·. ’―般廣為採用的技術， 合物等的南幸夺難姆：⑷有機溪化合物、有機氯化 f糸難燃劑，(b)有機磷系化合物，( 或（d)金屬氧化物中 物U)二乳化銻， 難燃性。 1種或2種以上難燃劑，藉此來提昇 【發明内容】 然而，使用前述難燃劑⑷〜(d)時，存在著以下的問題。 之二)：素系化合I於燃燒時由於會產生帶來環境負擔 之鹵化物，並非理想的難燃劑。 触（b)使用有機碌系化合物為難燃劑時，會有聚氧醋發泡 體強度劣化的問題’且可能會阻礙聚氨醋發泡體之生成反 應。 (c)三氧化銻，已確認出會造成環境負擔，並不適用。 ‘ （d)使用氫氧化鋁及氫氧化鎂般之金屬氫氧化物為難燃 劑時，完全不會發生前述環境負擔的問題。然而，為了滿 足例如UL94(弱電關係之密封材及防音材）所規定之難燃性 規格，則必須在聚氨酯發泡體的原料中混入大量的金屬氫 氧化物。這時’極可能會影響其作為密封材之有益物性， 例如會影響聚氨酯發泡體本來應展現之低硬度物性。1363079 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a flame retardant sealing material. In particular, the flame-retardant sealing material of the present invention has excellent sealing properties and flame retardancy, and can be used in a harsh environment such as a high-temperature environment, and is suitable for high-heating electronic devices and precision machines. By. [Prior Art] A display-like electrical device such as a mobile phone, a television, or a computer is provided with an input/output portion such as a liquid crystal display unit, a microphone unit, and a speaker unit. These input and output portions are provided at the outward opening of the electrical machine casing. Therefore, for example, in the case of the liquid crystal display unit, a sealing material is disposed between the periphery of the liquid crystal display unit and the frame to prevent dust from entering and leaking the backlight for liquid crystal display, and to prevent shaking between the frame and the frame. . In recent years, various types of electrical equipment represented by mobile phones have been highly functional and lightweight: The demand for sealing materials is also required to be small and thin. The material of the sealing material* is based on the fact that even if it is thin, it can fully exert the function of the sealing material, and it is suitable for polyurethane foam which is excellent in flexibility and low in hardness. Further, the polyoxy-lysate foam is suitable for use as a sealing material in an electric machine casing due to deterioration (deterioration) of the material and generation of gas. 'has a good' and forms an electronic machine. Therefore, in some cases, the sealing material composed of the polyurethane foam may have the sealing material characteristics as described above. However, the sealing material is formed into a sheet having a high specific surface area from an organic material, and is assembled in an electric machine because of such a machine. The heat generated during the operation may become a high temperature 丄 sealing material, which requires high flame retardancy. In the raw materials of the sealing material, the technology used in the sealing materials, such as the widely used technology, compounds, etc.: (4) organic brook compounds, organic chlorinated f flammable agents, (b) organophosphorus compounds, ( Or (d) metal oxide intermediate U) diemulsified oxime, flame retardant. One or two or more kinds of flame retardants are used to improve the content of the invention. However, when the flame retardants (4) to (d) are used, the following problems occur. Second): The compound I is not an ideal flame retardant because it produces a halide that causes environmental burden during combustion. When the (b) organic compound is used as a flame retardant, there is a problem that the strength of the polyoxyacetate foam is deteriorated, and the formation reaction of the polyurethane foam may be hindered. (c) Antimony trioxide has been identified as causing an environmental burden and is not applicable. ‘ (d) When a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used as a flame retardant, the above environmental burden is not caused at all. However, in order to satisfy the flame retardancy specifications prescribed by, for example, UL94 (a seal material and a soundproof material having a weak electrical relationship), it is necessary to mix a large amount of metal hydroxide in the raw material of the polyurethane foam. At this time, it is highly likely to affect its beneficial properties as a sealing material, for example, it may affect the low hardness properties that the polyurethane foam should exhibit.
又 ’ UL94，係美國 UNDERWRITERS LABORATORIES me.公司所制定及認可之電氣機器相關安全性規格。該 UL94規定之難燃性評價方法，係用圖5(a)、（b)所示之實 驗裝置40，以本生燈或梯瑞爾燃燒器44直接用火加熱於 1363079 金屬網42上所載置的試驗月41，測定該試驗片41之燃燒 距離及燃燒時間。UL94中，以圖5(a)、（b)所示之水平燃 燒試驗（Horizontal Burning Foamed Material Test)評價試驗 片41的難燃性(HFB規格）的情形，其評價係根據：當直接 用火加熱於150mm X 50mm長方形的試驗片41之長邊方向 一端時是否達成以下（i)、（ii)之任一方來進行，其中，條件 (0:從直接用火加熱的位置至沿試驗片41長邊方向離開 100mm的位置為止其燃燒速度未超過々ο mm/分，條件⑴）： 試驗片41著火後之火焰或燃燒在到達125mm之標記前已 消失。又，該125mm標記之設置位置，係從用火直接加熱 的位置起沿試驗片41長邊方向離開125mm處。 為克服前述課題而達成所期望之目的，本發明之難燃 性密封材，係具備由混合物成形而得之彈性片丨2，該混合 物具有：多元醇及異氰酸酯所構成之主原料、包含整泡劑 及金屬氫氧化物16之副原料、及造泡用氣體。且其特徵 在於，相對於多元醇100重量份，係混合25〜5〇重量份之 金屬虱氧化物16，且以可和異氰酸酯反應的物質當作副原 料之稀釋用溶劑。又，該密封材係滿足UL94所規定之難 燃性HBF規格，且其25%壓縮負荷為〇.〇3Mpa以下。 依據本發明之難燃性密封材，其具備優異的密封性及 難燃性，可使用於高溫環境氣氛般之嚴酷環境下，且適用 於尚發熱性之電子機器與精密機器。 其次，針對本發明的難燃性密封材之較佳實施例，參 照所附圖式進行說明。本案發明人針對難燃性密封材進行 1363079 深入研究的結果獲得以下認知。亦即，聚氨酯發泡體中， 會降低難燃性之未反應單體及低分子寡聚物（受熱揮發而成 為可燃性氣體成分）之含量極少。因此，聚氨酯發泡體適用 於达封材的原料。又，若採用機械造泡法，可避免使用高 揮發性低分子物質之胺觸媒，且能抑制整泡劑（製造發泡體 時一定會用到）之揮發。藉此所得之難燃性密封材，不僅可 減低金屬氫氧化物之混合量，且能獲得充分的難燃性與密 封性。 又，本發明中關於難燃性密封材之特徵物性、即難燃 性與岔封性，係分別以UL94所規定之HBF規格及25%壓 縮負荷（以下稱 25〇/〇CLD(C〇mpression Load Deflecti〇n))來 規定。又，關於難燃性，係根據是否滿足HBF規格來評價； 關於密封性，係根據是否滿足柔軟性指標之25%cld在 〇.〇3Mpa以下來進行評價。 難燃性密封材1 〇，如圖.丨所示，係由彈性片12與基 材膜14所構成；該彈性片12，係由具備緩衝性、密封性= 柔軟性及形狀追隨性等各種物性之發泡體所構成；該基材 膜14,係積層.於彈性片12之一面，用來提昇難燃性二封 材10之構造強度。該彈性片12係以公知的機械造泡法來 裝造。具體’而言，係將多元醇及異氰酸酯所構成之主原料、 包含整泡劑及金屬氫氧化物（難燃劑）16之副原料、及造泡 用氣體加以混合，調整成發泡體原料M後，將該發泡體原 成形為片狀。在彈性片12内部，金屬氣氧化物呈均 貝分散狀態（參照圖丨）。關於機械造泡法之詳細說明，例 1363079 如記載於日本特公昭53-9735號公報。簡而言之，所謂機 械造泡法，係在液狀材料導入氣體，以機械方式加以混合， 而製造發泡體。 如此般製得彈性片12之物性值中，關於用來評價密射 性之柔軟性指標’係測定（1)25%Cld在0.03Mpa以下。 25%CLD ’代表施加25%的物理壓縮時所需的負荷，即施 加250/〇物理壓縮時彈性片12的硬度。又，彈性片12之另 一物性值，關於用來評價密封性、難燃性雙方之指標，孫 測定（2)密度在240〜500kg/m3的範圍。關於彈性片u之其 他物性值’較佳為測定（3)厚度在〇3〜3 〇mm的範圍。 在此’右25%CLD超過〇.〇3Mpa，由於彈性片12之柔 軟性降低而無法發揮充分的密封性。若密度未達 240kg/m3 ’由於彈性片12中的氣泡呈稀疏狀態，其與空氣 的接觸面積増大而難以滿足UL94規定之HBF規格。相反 地’若密度超過500kg/m2，由於25%CLD也會同時增大， 彈性片12之密封性會降低。若厚度未達〇.3mm，除彈性 片1 2之饮封性難以充分發揮外，由於其對直接用火加熱 的著火性昇高，難以滿足UL94規定之HBF規格。相反地， 若厚度超過3.0mm，由於過厚而難以組裝於設置空間受限 之行動電話等的小型製品。 再者，彈性片12所要求之上述以外的特性值中，關於 貝難燃性之指標，必須滿足（4)UL94所規定之規格。 為提高彈性片12之難燃性，可在發泡體原料M中，混合 既定比例之金屬氫氧化物〗6作為難燃劑，並混合多元^ 1363079 :可和異氣酸酷反應之物質作為稀釋用溶劑，而藉此來達 彈性片12之製造，如前述般，係 ^ ^ ^ ^ _ 通常製造聚氨酯發 /包體的情形相同’使用多元醇及里羞缺& 畔久，、氰酸酯所構 料、包含整泡劑及金屬氮氧化物16(難燃劑)之副片料。這 時’視需要可使用擇自發泡劑 '交聯劑、 ^ s , P %可塑劑及觸媒中 之至少一種副原料。在此，彈性片12中夕夕 ^之多元醇及里氰 酸醋含量，較佳為分別設定成20〜45重眚〇/B 、 …</ STRONG> UL94 is the safety standard for electrical equipment developed and approved by UNDERWRITERS LABORATORIES me. The flame retardancy evaluation method specified in UL94 is directly heated by fire on the 1363079 metal mesh 42 by the Bunsen burner or the Tieril burner 44 using the experimental device 40 shown in Figs. 5(a) and 5(b). On the test month 41 placed, the burning distance and the burning time of the test piece 41 were measured. In UL94, the flame retardancy (HFB specification) of the test piece 41 was evaluated by the Horizontal Burning Foamed Material Test shown in Figs. 5(a) and (b), and the evaluation was based on: when using the fire directly Whether or not one of the following (i) and (ii) is achieved when heated to one end in the longitudinal direction of the 150 mm X 50 mm rectangular test piece 41, wherein the condition (0: from the position directly heated by the fire to the position along the test piece 41) The burning speed of the long side direction away from the position of 100 mm does not exceed 々ο mm/min, condition (1)): The flame or burning of the test piece 41 after the ignition has disappeared before reaching the mark of 125 mm. Further, the position where the 125 mm mark is placed is 125 mm away from the longitudinal direction of the test piece 41 from the position where it is directly heated by fire. In order to achieve the desired object in order to overcome the above problems, the flame-retardant sealing material of the present invention comprises an elastic sheet 2 obtained by molding a mixture having a main raw material composed of a polyol and an isocyanate, and comprising a whole foam. The auxiliary material of the agent and the metal hydroxide 16 and the gas for foaming. Further, it is characterized in that 25 to 5 parts by weight of the metal cerium oxide 16 is mixed with 100 parts by weight of the polyol, and a substance reactive with isocyanate is used as a solvent for dilution of the by-product. Further, the sealing material satisfies the flame retardant HBF standard prescribed by UL94, and the 25% compression load is 〇.3Mpa or less. According to the flame-retardant sealing material of the present invention, it has excellent sealing properties and flame retardancy, and can be used in a harsh environment such as a high-temperature environment, and is suitable for electronic devices and precision machines that are still heated. Next, a preferred embodiment of the flame-retardant sealing material of the present invention will be described with reference to the accompanying drawings. The inventors of the present invention obtained the following findings on the results of intensive studies on the flame retardant sealing material 1363079. In other words, in the polyurethane foam, the unreacted monomer and the low molecular oligomer (which are volatilized by heat to form a combustible gas component) which are low in flame retardancy are extremely small. Therefore, the polyurethane foam is suitable for use as a raw material for the sealing material. Further, if the mechanical foaming method is employed, the use of an amine catalyst having a high volatility and a low molecular weight can be avoided, and the volatilization of the foam stabilizer (which must be used when the foam is produced) can be suppressed. The flame-retardant sealing material thus obtained can not only reduce the amount of metal hydroxide mixed, but also obtain sufficient flame retardancy and sealing properties. Further, in the present invention, the physical properties of the flame-retardant sealing material, that is, the flame retardancy and the sealability, are respectively HBF specifications and 25% compression load as defined by UL94 (hereinafter referred to as 25 〇/〇CLD (C〇mpression). Load Deflecti〇n)) to stipulate. In addition, the flame retardancy is evaluated based on whether or not the HBF standard is satisfied. The sealing property is evaluated based on whether or not the 25% cld of the flexibility index is satisfied at 〇.3Mpa or less. The flame-retardant sealing material 1 〇 is composed of an elastic sheet 12 and a base film 14 as shown in Fig. ;; the elastic sheet 12 is provided with various cushioning properties, sealing properties, flexibility, and shape followability. The substrate film 14 is a laminated layer on one side of the elastic sheet 12 for enhancing the structural strength of the flame-retardant two-pack material 10. The elastic sheet 12 is assembled by a known mechanical foaming method. Specifically, the main raw material composed of a polyhydric alcohol and an isocyanate, a secondary raw material including a foam stabilizer, a metal hydroxide (flammable agent) 16, and a gas for foaming are mixed and adjusted into a foam raw material. After M, the foam was originally formed into a sheet shape. Inside the elastic sheet 12, the metal gas oxide is in a state of uniform dispersion (see Fig. 丨). For a detailed description of the mechanical foaming method, the example 1363079 is described in Japanese Patent Publication No. Sho 53-9735. In short, the mechanical foaming method is to introduce a gas into a liquid material and mechanically mix it to produce a foam. In the physical property values of the elastic sheet 12 thus obtained, the flexibility index for evaluating the adhesion property was measured as (1) 25% Cld was 0.03 MPa or less. 25% CLD' represents the load required to apply 25% of physical compression, i.e., the hardness of the elastic sheet 12 when 250/〇 physical compression is applied. Further, the other physical property value of the elastic sheet 12 is in the range of 240 to 500 kg/m3 in terms of the index for evaluating both the sealing property and the flame retardancy. The other physical property values of the elastic sheet u are preferably measured in the range of (3 to 3 〇mm. Here, the right 25% CLD exceeds 〇.〇3Mpa, and the flexibility of the elastic sheet 12 is lowered to prevent sufficient sealing. If the density is less than 240 kg/m3', since the air bubbles in the elastic sheet 12 are sparse, the contact area with air is large, and it is difficult to satisfy the HBF specification of UL94. On the contrary, if the density exceeds 500 kg/m2, since the 25% CLD is also increased at the same time, the sealing property of the elastic sheet 12 is lowered. If the thickness is less than 33 mm, it is difficult to fully exhibit the sealing property of the elastic sheet 12, and it is difficult to satisfy the HBF specification of UL94 because of the increased ignitability of heating directly by fire. On the other hand, when the thickness exceeds 3.0 mm, it is difficult to assemble a small product such as a mobile phone having a limited installation space because it is too thick. Further, among the characteristic values other than the above required for the elastic sheet 12, it is necessary to satisfy the specifications specified in (4) UL94 for the index of the flame retardancy of the shell. In order to improve the flame retardancy of the elastic sheet 12, a predetermined proportion of the metal hydroxide -6 can be mixed as a flame retardant in the foam raw material M, and a plurality of materials 1363079 can be mixed as a substance which reacts with the isogas acid. The solvent for dilution is used to obtain the manufacture of the elastic sheet 12, as described above, in the case where the polyurethane hair/envelope is usually produced in the same manner as in the case of using a polyol and a smear, and a long time, cyanide The ester material composition, the sub-sheet containing the foam stabilizer and the metal oxynitride 16 (flammable agent). At this time, at least one of the auxiliary materials selected from the foaming agent 'crosslinking agent, ^ s , P % plasticizer and catalyst may be used as needed. Here, the content of the polyol and the cyanoic acid vinegar in the elastic sheet 12 is preferably set to 20 to 45 眚〇/B, respectively.
里里/〇及25〜35重量 %左右。又，彈性片12中之整泡劑含量（包含稀釋用溶劑） 較佳為設定成2〜3重量％，交聯劑含量較佳為設定成8〜15 重量％，觸媒含量較佳為設定成3〜5重量％。又在製造 該彈性片12時，機械造泡法所用之非活性氣體般之造泡 用氣體的混合量，相對於該造泡用氣體除外之原料總體積 100，較佳為50〜200體積％左右。 關於金屬氫氧化物1 6，可使用經加熱其分子内之經基 (·〇Η)會解離而產生水之氫氧化鋁及氫氧化鎂。金屬氫氧化 物16之混合量’相對於多元醇1〇〇重量份，較佳為25〜5〇 重量份，更佳為30〜3 5重量份。其混合量未達25重量份Lili / 〇 and 25 ~ 35 wt% or so. Further, the foaming agent content (including the solvent for dilution) in the elastic sheet 12 is preferably set to 2 to 3% by weight, and the crosslinking agent content is preferably set to 8 to 15% by weight, and the catalyst content is preferably set. It is 3 to 5 wt%. Further, when the elastic sheet 12 is produced, the mixing amount of the inert gas-like foaming gas used in the mechanical foaming method is preferably 50 to 200% by volume based on the total volume of the raw material 100 excluding the foaming gas. about. Regarding the metal hydroxide 16, it is possible to use aluminum hydroxide and magnesium hydroxide which generate water by dissociating the radical (·〇Η) in the molecule. The compounding amount of the metal hydroxide 16 is preferably 25 to 5 parts by weight, more preferably 30 to 3 parts by weight, per part by weight of the polyol. The amount of the mixture is less than 25 parts by weight
時無法發揮所期望的難燃性，相反地超過5〇重量份時， 難燃性密封材1 〇變硬、或出現脆性而使密封性降低。 金屬氩氧化物1 6之平均粒徑，較佳為1 0〜1 〇〇 β m，更 佳為20〜60以m之範圍。金屬氫氧化物1 6之平均粒徑未達 10 μ m時，發泡體原料M之粘度變高，或發泡體原料M 之含水率變高而產生水與異氰酸酯之發泡反應，這時要以 10 1363079 法製造出適當的彈性片12會有困難。相反地， 仆你氫氧化物16之平均粒徑超過丨_ m，將金屬氫氧 ./ 混合於發泡體原料Μ時金屬氫氧化物16容易產生 ’儿降’如此要在彈性片12内部使金屬氫氧化物16良好地 分散會有困難。產生今 ' 金屬虱氧化物16沉降之發泡體原料 Μ所製造出之難燃性衆 _ ，… 封材10，會發生依部位其難燃性不 同之問題。又’雖有可能在該金屬氫氧㈣16沉降前就 完成難燃性密封材10《製造，但這時須對製造時間加以 限制，而有產生製造上的不便之虞。 關於整泡劑’適於採用公知之矽酮系整泡劑。該整泡 劑，在以機械造泡法製造聚氨酯發泡體時乃不可或缺者， 但其為低分子物質故易燃燒’乃造成彈性# 12難燃性降 低之-大要因。又’碎酮系難燃劑之枯度非^冑，故使用 時必須經稀釋用的溶劑稀釋。用以稀釋整泡劑之溶劑，可 採用多元醇等可和異氰酸酯反應之物質。 使用分散於多元醇（稀釋用溶劑）之整泡劑來製造聚氨 酯發泡體12時，稀釋介質之多元醇會和彈性片12主原料 之異氰酸酯反應而形成聚氨酯分子，而將整泡劑抓入該聚 氨酯分子内。其結果，製得之彈性片12中，可防止整泡 劑之揮發而減少難燃性降低之主因。稀釋整泡劑時之溶劑 量，較佳為設定成整泡劑含量在3〇〜7〇重量％的範圍。整 泡劑含量未達30重量％時，製造彈性片12時之整泡功能 降低。相反地整泡劑含量超過7〇重量％時，整泡劑分散液 之粘度變高，而使製造時之操作性變差。 11 1363079 又，一般用來稀釋矽酮系整泡劑之溶劑，較佳為採用 烧基苯等常溫下粘性低之液狀低沸點物質。然而，這種低 沸點物質因溶易揮發，可能會影響製品之難燃性。這種低 沸點物質，不僅包含稀釋用溶劑，也包含主原料之多元醇 合成用之單體及氧化防止劑等各種物質。於是’作為滿足 UL94所規定之難燃性HBF規格的—條件係定義彈性片 12中可被丙酮溶解物質（以下稱被溶解物質）含量。本發明 中，彈性片丨2中之被溶解物質含量，較佳為5 〇重量^以 下。本發明人確認出，該被溶解物質含量超過5 〇重量％ 時，就算金屬氫氧化物16之混合量及整泡劑相關之所有 條件均滿足，仍要法滿足動4所規定之難燃性咖規格。 該被溶解物質之含量，例如藉由測定以丙酮萃取彈性 片12時的萃取率、即丙嗣萃取率來求出。丙綱萃取率之 具體測定方法的-例列舉於後述的實驗例。又，去稀釋整 泡劑之溶劑係使用貌基苯等低沸點物質時，由於: 物質在彈性片12内部會以聚氛酿分子構造外的游離形能 存在，溶劑可能會遷移至與彈性# 12接觸之框體等料 而產生遷移性之問題。因此’用來稀釋整泡劑之溶劑，藉 ==可與異氰酸'反應之物f，則其大幅抑制 則述遷移性問題之效果是可期待.的。 基材膜14,如前述般，為了提昇難燃性密封材10之 構造強度而使製品的操作性良好，係積層於彈性片Μ而 形成一體。該基材膜丨4，如後 於f驻f 料之裊造方法所記載，亦當In the case where the desired flame retardancy is not exhibited, when the amount exceeds 5 parts by weight, the flame retardant sealing material 1 becomes hard or brittle and the sealing property is lowered. The average particle diameter of the metal argon oxide 16 is preferably from 10 to 1 〇〇 β m , more preferably from 20 to 60 in the range of m. When the average particle diameter of the metal hydroxide 16 is less than 10 μm, the viscosity of the foam raw material M becomes high, or the water content of the foam raw material M becomes high, and a foaming reaction between water and isocyanate occurs, and at this time, It is difficult to manufacture a suitable elastic sheet 12 by the method of 10 1363079. Conversely, if the average particle size of the hydroxide 16 exceeds 丨_m, the metal hydroxide 16 is easily produced when the metal hydroxide is mixed with the foam material, so that it is inside the elastic sheet 12. It is difficult to disperse the metal hydroxide 16 well. The flame retardant material produced by the current metal ruthenium oxide 16 sedimentation _, _,... The sealing material 10 has different problems depending on the flame retardancy of the part. Further, although it is possible to complete the manufacture of the flame-retardant sealing material 10 before the deposition of the metal hydroxide (4) 16, it is necessary to limit the manufacturing time, and there is a manufacturing inconvenience. As the foam stabilizer, a known ketone-based foam stabilizer is suitably used. The foam stabilizer is indispensable in the production of a polyurethane foam by a mechanical foaming method, but it is a low molecular substance and is easily burned, which causes a decrease in the flame retardancy of the elastic #12. Further, the degree of dryness of the ketone-based flame retardant is not dilute, so it must be diluted with a solvent for dilution. The solvent for diluting the foaming agent may be a substance which reacts with an isocyanate such as a polyol. When the polyurethane foam 12 is produced by using a foam stabilizer dispersed in a polyol (diluting solvent), the polyol of the dilution medium reacts with the isocyanate of the main raw material of the elastic sheet 12 to form a polyurethane molecule, and the foam stabilizer is caught. The polyurethane is intramolecular. As a result, in the obtained elastic sheet 12, the volatilization of the foam stabilizer can be prevented, and the main cause of the decrease in flame retardancy can be reduced. The amount of the solvent when the foam stabilizer is diluted is preferably set to a range of from 3 Torr to 7 Torr by weight of the foam stabilizer. When the content of the foaming agent is less than 30% by weight, the foaming function at the time of producing the elastic sheet 12 is lowered. On the other hand, when the content of the foam stabilizer exceeds 7% by weight, the viscosity of the foam stabilizer dispersion becomes high, and the workability at the time of production is deteriorated. 11 1363079 Further, a solvent which is generally used for diluting an anthrone-based foaming agent is preferably a liquid low-boiling substance having a low viscosity at a normal temperature such as benzoylbenzene. However, such low boiling materials are volatile due to dissolution and may affect the flame retardancy of the product. Such a low-boiling substance includes not only a solvent for dilution but also a monomer such as a monomer for synthesizing a polyol of a main raw material and an oxidation preventing agent. Then, as a condition that satisfies the flame retardant HBF specification prescribed by UL94, the content of the acetone-dissolvable substance (hereinafter referred to as dissolved matter) in the elastic sheet 12 is defined. In the present invention, the content of the dissolved substance in the elastic sheet 2 is preferably 5 Å or less. The present inventors have confirmed that when the content of the dissolved substance exceeds 5% by weight, even if the mixing amount of the metal hydroxide 16 and all the conditions related to the foam stabilizer are satisfied, the flame retardancy specified in the motion 4 is still satisfied. Coffee specifications. The content of the dissolved substance is determined, for example, by measuring the extraction ratio when the elastic sheet 12 is extracted with acetone, that is, the extraction ratio of propylene. The example of the specific measurement method of the extraction rate of the C-type is listed in the experimental example mentioned later. Further, when the solvent for diluting the foaming agent is a low-boiling substance such as phenoylbenzene, the substance may be present in the elastic sheet 12 in a free form other than the molecular structure of the polymer, and the solvent may migrate to the elasticity. 12 Contact the frame and other materials to cause migration problems. Therefore, the solvent used to dilute the foaming agent can be expected to be greatly suppressed by the fact that the substance f which can react with the isocyanate is greatly suppressed. As described above, in order to improve the structural strength of the flame-retardant sealing material 10, the base film 14 is excellent in handleability of the product, and the laminated layer is integrally formed on the elastic sheet. The substrate film 4, as described in the method of manufacturing the material after the f, is also
作1 &裝置30之發泡體原料M 疋移送介質。因此，基材 12 1363079 膜14必須具備：足夠的物理強度以對抗輥機構所施加 之張力，及足夠的耐熱性以承受為使發泡體原料M硬化之 隧道式加熱爐38之加熱。該基材膜14之材質為了比聚 乙烯(PE)、聚丙烯(PP)等汎用樹脂更不易熱收縮，較佳為 使用聚對苯二甲酸乙二醇酯（PET)等樹脂。又，基材膜Μ 之厚度雖依材質而變動，但較佳為設定在12〜5〇〇“m，更 2為設定在25〜125以爪左右。這種厚度的基材臈14，就 异積層於彈性片12也不會對難燃性密封材1〇的密封性產The foam material M 疋 transfer medium of the 1 & device 30 is used. Therefore, the substrate 12 1363079 film 14 must have sufficient physical strength to withstand the tension applied by the roller mechanism and sufficient heat resistance to withstand the heating of the tunnel furnace 38 for hardening the foam material M. The material of the base film 14 is more resistant to heat shrinkage than a general-purpose resin such as polyethylene (PE) or polypropylene (PP), and a resin such as polyethylene terephthalate (PET) is preferably used. Further, although the thickness of the base film 变动 varies depending on the material, it is preferably set to 12 to 5 〇〇 "m, and 2 is set to about 25 to 125 claws. The substrate 这种 14 of this thickness is The outer laminate does not seal the flame retardant sealing material 1 to the elastic sheet 12
生不良影響。X ’例如使用成型模具來成形難燃性密封材 W時’並不需要基材冑14，而能製得圖2所示之僅由彈 性片1 2構成之難燃性密封材1 。 【實施方式】 (製造方法之一例） 本實施例之難燃性密封材10的較佳製造裝置之一例、 及使用該製造裝置之難燃性密封材i 0的製造方法，在以 下作說明。難燃性密封# 1〇之製造方法，如圖3所示係 由原料準備步驟si、原料供給及成形步驟s2、加熱步驟 S3'最終步驟S4等所構成。該難燃性密封材1()，係以圖 4所示的製造裝置30來製造。 該製造裝置30，為了獲得供實施機械造泡法之聚氦酯 發泡體的發泡體原料M，係具備用來混合主原料、各種副 原料及造泡用氣體之混合部31。該製造裝置3〇，係具備 由供給輥32a與製品回收輥32b所構成之輥機構32，其使 13 ^63079Bad effects. For example, when the flame-retardant sealing material W is formed by using a molding die, the substrate 胄 14 is not required, and the flame-retardant sealing material 1 composed only of the elastic sheet 1 2 shown in Fig. 2 can be obtained. [Embodiment] (An example of the production method) An example of a preferred apparatus for producing the flame-retardant sealing material 10 of the present embodiment and a method for producing the flame-retardant sealing material i 0 using the production apparatus will be described below. The manufacturing method of the flame-retardant seal #1 is composed of a raw material preparation step si, a raw material supply and molding step s2, a heating step S3', a final step S4, and the like, as shown in Fig. 3 . This flame-retardant sealing material 1 () is produced by the manufacturing apparatus 30 shown in Fig. 4 . In order to obtain the foam raw material M for carrying out the polydecyl ester foam of the mechanical foaming method, the manufacturing apparatus 30 includes a mixing portion 31 for mixing the main raw material, various auxiliary materials, and a gas for foaming. This manufacturing apparatus 3 is provided with a roller mechanism 32 composed of a supply roller 32a and a product recovery roller 32b, which makes 13 ^ 63079
用未圖示之驅動源來將發泡體原料M 膜14予以移送。由排出嘴34 送"質、即基材 膜 ^由排出嘴34將發泡體原料M供給至基材 厚 。在排出嘴34的下游側設有到刀塗布機等的製口 1機構36,以將發泡體原料M成形為既定 =又在該製品厚控制機構36之下游側設有隨道式加鼓爐 4處雖在平面上使發泡體原料m進行反應與硬化， -在既疋的成形模内或脫模紙上進行反應及硬化亦可。 混合部31係具備··主®斜夕之_ e 科之夕70醇用的容器3U，主 料之異㈣酯用的容器31b，副原料之整泡劑用的容器 副原料之金屬氫氧化物16用的容器31de視 可設置整泡劑及金屬氫氧化物16以外的副原料用的容 二又，處合部31係具備：供充填造泡用氣體之容器31e、 各合态31a〜31e内的原料，在控制下供給 至混合機3 1 f，並在混合機3 1 f内混合。 鞔機構32 ’在對基材膜14施加張力下將基材膜μ供 給至製造線’並回收所製得之難燃性密封# 10。在製造線 上’於供給輥32a與製品回收輥奶之間，係設有排出嘴 34、製品厚控制機構36及随道式加熱爐38。基材膜“播 繞於供給輕32a上，該供給輥32a在控制下將基材膜丨斗向 製把線送出。排出嘴34之一端連接於混合部3 1，在控制 下將"工σ。卩3】混合後之發泡體原料μ排出至移送至 製造線上的基材膜14上面。 移送至 在混合部31實施之原料準備步驟S1，係依習知公知 的方法準備好主原料、副原料及造泡用氣體後，使用混合 14 ^63079 重量伤犯合金屬觸媒(辛酸亞錫鹽ι重量份、矽酮系之 查泡劑3重置份（包含稀釋用的溶劑卜金屬氯氧化物！ 6(其 混合量參照表！及表2)，製得混合物。對該混合物，將氮 乳（造泡用氣體）與異氰㈣指數"七之聚異氰酸醋（粗 刪’卿含量31%)以Q」NL/分鐘的流量進行剪切混合， 製得發泡體原料M。通過排出冑34,將該發泡體原料M 排出至既定厚度的基材膜14(pET製）上。這時，基材膜Μ 係以破親機構32施加張力的狀態由供給輕…連續地供 給。又，該發泡體料M，係以製造後的彈性片12密度 成為表1及表2數值的方式從排出嘴34供給，並以製造 後的彈性片12厚度成為表1及表2數值的方式以製品厚 控制機構36成形。接著，將積層於基材膜14上之發泡體 原料Μ在隧道式加熱爐38内以15〇〜2〇(Γ(：加熱！〜3分鐘， 使其反應及硬化。其結果，製得在基材膜14上面積層有 彈性片12之難燃性密封材。製得之難燃性密封材以製品 回收輥32b來回收。 所使用之金屬氳氧化物丨6及整泡劑如下所示。 金屬氫氧化物：氫氧化铭（昭和電工製，商品名海 地萊特H-2 1 (平均粒徑25 " m) •整泡劑 (A) Osi Specialties製，商品名在稀釋用溶劑 之多元酵中，含有50重量％之聚二.曱基矽氧烷及聚氧化烯） (B) Osi Specialties製，商品名L_5614(在稀釋用溶劑之 烷基苯中，含有50重量％之聚二曱基矽氧烷及聚氧化烯） UL94所規定之HBF規格來 τ彳月5式驗片4〗之難燃 •溶解於丙嗣之物皙旦,工 ’·‘、 〈物質里(丙酮萃取率）：將彈性片 試驗片（lg)置於索克斯累牲 ,7矛兄所累特卒取器，在該萃取器内使丙酮 加熱迴流3小時以將丙酮可溶解的物質萃取後，將該萃取 物乾燥並測定乾燥重量。依據： 丙嗣萃取率（％)=萃取物之乾燥重量（g)/置於索克斯累 特萃取器前之試驗片重量The foam raw material M film 14 is transferred by a driving source (not shown). The foam material W is supplied from the discharge nozzle 34 to the substrate, and the foam material M is supplied to the substrate to be thick. On the downstream side of the discharge nozzle 34, a nozzle 1 mechanism 36 to a knife coater or the like is provided to shape the foam material M to be predetermined = and a drum type drum is provided on the downstream side of the product thickness control mechanism 36. In the furnace 4, the foam raw material m is reacted and hardened on a flat surface, and the reaction or hardening may be carried out in a molding die or a release paper. The mixing unit 31 is provided with a container 3U for alcoholic alcohol 70, a container 31b for the main ingredient (tetra) ester, and a metal hydroxide for the container auxiliary material for the foam of the auxiliary material. The container 31 for the object 16 is provided with a container for the auxiliary material other than the foam stabilizer and the metal hydroxide 16. The container 31 is provided with a container 31e for filling the gas for foaming, and each of the joints 31a to 31a. The raw material in 31e is supplied to the mixer 3 1 f under control and mixed in the mixer 3 1 f. The crucible mechanism 32' supplies the base film μ to the manufacturing line under the tension applied to the base film 14, and recovers the produced flame-retardant seal #10. Between the supply roller 32a and the product recovery roller milk, a discharge nozzle 34, a product thickness control mechanism 36, and a follower type heating furnace 38 are provided on the manufacturing line. The substrate film is "spun on the supply light 32a, and the supply roller 32a feeds the substrate film bucket to the handle line under control. One end of the discharge nozzle 34 is connected to the mixing portion 3 1, and under control Σ.3] The foam raw material μ after mixing is discharged onto the substrate film 14 transferred to the manufacturing line. The raw material preparation step S1 is carried out in the mixing unit 31, and the main raw material is prepared by a conventionally known method. After the auxiliary materials and the gas for foaming, use a mixture of 14 ^ 63079 weight of the metal catalyst (the amount of stannous octoate 1 part by weight, the ketone type of the foaming agent 3 reset part (including the solvent for dilution) Oxychloride! 6 (mixing amount refers to the table! and Table 2) to prepare a mixture. For the mixture, nitrogen milk (gas for foaming) and isocyanide (four) index " seven polyisocyanuric acid vinegar The "clear content of 31%" was shear-mixed at a flow rate of Q"NL/min to obtain a foam raw material M. By discharging the crucible 34, the foam raw material M was discharged to the substrate film 14 of a predetermined thickness ( In the case of the pET system, at this time, the base film is continuously supplied by the state in which the breaking mechanism 32 applies tension...continuously Further, the foamed material M is supplied from the discharge nozzle 34 so that the density of the elastic sheet 12 after the production becomes the values of Tables 1 and 2, and the thickness of the elastic sheet 12 after manufacture becomes Table 1 and Table 2. The numerical method is formed by the product thickness control mechanism 36. Next, the foam raw material laminated on the base film 14 is kneaded in the tunnel type heating furnace 38 by 15 〇 2 〇 (: heating: ~3 minutes, As a result, a flame-retardant sealing material having an elastic sheet 12 in the area of the base film 14 is obtained, and the obtained flame-retardant sealing material is recovered by the product recovery roller 32b. The oxide 丨6 and the foam stabilizer are as follows. Metal hydroxide: Hydroxide (manufactured by Showa Denko, trade name: Haitian Wright H-2 1 (average particle size 25 " m) • Foaming agent (A) Osi Manufactured by Specialties, the product name is 50% by weight of polydidecyloxane and polyoxyalkylene in the dilute solution of the solvent for dilution. (B) Osi Specialties, trade name L_5614 (alkyl group in solvent for dilution) Benzene containing 50% by weight of polydidecyl fluorene oxide and polyoxyalkylene) HBF as defined by UL94格 彳 彳 5 5 式 式 式 式 式 • • • • • • • • • • • • • • • • • • • • • 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解In the extractor, the acetone was heated and refluxed for 3 hours to extract the acetone-soluble substance, and the extract was dried and the dry weight was determined. (%) = dry weight of extract (g) / test piece weight placed before Soxhlet extractor
來异出丙嗣萃取率。 •是否含烧基笨··將上述萃取物以氣體層析質量分析 裝置（GC-MS，島津製作所之商品名QP-5000)進行質譜分 析並予以評價。Come out of the extraction rate of propylene. • Whether or not the above-mentioned extract was analyzed by mass spectrometry using a gas chromatography mass spectrometer (GC-MS, trade name of Shimadzu Corporation, QP-5000).
18 1363079 (表i) 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 彈性片厚度(mm) 0,3 0.4 0.5 <- <- 1.0 1.5 3.0 密度(kg/m3) 360 360 240 320 500 360 320 240 整泡劑種類 A <- <- 金屬氫氧化物之 混合量(重量份） 30 <- <- <- <- 20 30 结果 25%CLD(MPa) 0.012 0.012 0.007 0.011 0.030 0.012 0.011 0.007 難燃性(〇、X) 〇 <— <— <- — <- <- 丙酮萃取率(％) 4.5 4.7 4.0 5.0 4.1 4.7 4.5 4.0 是否含烷基苯 否 <- <— <- <- <- <- <— 綜合評價 〇 - <- 表中之25%CLD代表25%壓縮負荷。 表中之整泡劑種類，A代表L-5617，B代表L-5614。 19 1363079 (結果） 根據表1及矣9 —p + 表2可確認出，藉由將彈性片丨2的各 值控制在本發明所Μ中 Μ 斤°又疋之靶圍内，可製得兼具難燃性 封性之難燃性密封材。 、在 【圖式簡單說明】 圖1顯不將本發明較佳實施狀難燃性密封材局部切 除之立體圖。 圖2顯不未具備基材膜之難燃性密封材之立體圖。 圖3顯示實施例的難燃性密封材之製造方法之步％ 圖。 圖4顯示用來製造實施例的難燃性密封材之製造 〆例。 圖5⑷顯示用來實施.動4户斤規定之難燃性試驗的實 驗裝置整體之立體圖；圖5⑻顯㈣實驗裝置在試驗片附 近之擴大圖。 【主要.元件符號說明】 10.· •難燃性密封材 12·. •彈性片 14.. •基材膜 16·. •金屬氩氧化物 30- •製造裝置 31.. •混合部 21. 1363079 31a〜31e·"容器 3 If···混合機 32…輥機構 3 2 a…供給輥 32b···製品回收輥 34…排出嘴 36…製品厚控制機構 38…隧道式加熱爐 40…實驗裝置 41…試驗片 4 2…金屬網 44·..本生燈或梯瑞爾燃燒器 2218 1363079 (Table i) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Elastic sheet thickness (mm) 0,3 0.4 0.5 <- <- 1.0 1.5 3.0 Density (kg/m3) 360 360 240 320 500 360 320 240 Foaming agent type A <- <- metal hydroxide compounding amount (parts by weight) 30 <- <- <- <- 20 30 Results 25% CLD (MPa) 0.012 0.012 0.007 0.011 0.030 0.012 0.011 0.007 Flame retardancy (〇, X) 〇 < - < - <- - <- <- Acetone extraction rate (%) 4.5 4.7 4.0 5.0 4.1 4.7 4.5 4.0 Whether or not alkylbenzene is contained <- <- <- <- <- <- <- Comprehensive evaluation〇- <- 25% of CLD in the table represents 25% compression load . The type of foam stabilizer in the table, A represents L-5617, and B represents L-5614. 19 1363079 (Results) According to Table 1 and 矣9 - p + Table 2, it can be confirmed that the values of the elastic sheet 丨 2 can be controlled by controlling the respective values of the elastic sheet 丨 2 in the target circumference of the present invention. A flame retardant sealant that combines a flame retardant seal. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view showing a partially cutaway flame retardant sealing material of the preferred embodiment of the present invention. Fig. 2 is a perspective view showing a flame-retardant sealing material of a substrate film. Fig. 3 is a view showing a step % of a method for producing a flame-retardant sealing material of the embodiment. Fig. 4 shows an example of the manufacture of a flame-retardant sealing material used in the production of the examples. Fig. 5 (4) shows a perspective view of the entire experimental apparatus for carrying out the flame retardancy test prescribed by the mobile unit; Fig. 5 (8) shows an enlarged view of the experimental apparatus in the vicinity of the test piece. [Main. Description of component symbols] 10.· • Flame-retardant sealing material 12·. • Elastic sheet 14: • Substrate film 16·. • Metal argon oxide 30- • Manufacturing device 31.. • Mixing unit 21. 1363079 31a to 31e·"Container 3 If···Mixer 32...Roll mechanism 3 2 a...feed roller 32b···product recovery roller 34...discharge nozzle 36...product thickness control mechanism 38...tunnel heating furnace 40... Experimental apparatus 41...Test piece 4 2...Metal mesh 44·.Bunsen burner or Tireyer burner 22
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003413831A JP4544853B2 (en) | 2003-12-11 | 2003-12-11 | Method for producing flame retardant sealing material |
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| TW200519163A TW200519163A (en) | 2005-06-16 |
| TWI363079B true TWI363079B (en) | 2012-05-01 |
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| TW093137114A TWI363079B (en) | 2003-12-11 | 2004-12-02 | Flame retardant seal |
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| JP (1) | JP4544853B2 (en) |
| KR (1) | KR101133148B1 (en) |
| CN (1) | CN100393805C (en) |
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| CN101017965B (en) * | 2007-02-14 | 2011-07-06 | 上海市电力公司 | A blocking technology of SF6 gas insulation power device leakage |
| JP5479174B2 (en) * | 2009-03-24 | 2014-04-23 | 株式会社イノアックコーポレーション | Polyurethane foam laminate, method for producing the same, and gasket |
| JP5660975B2 (en) * | 2011-05-27 | 2015-01-28 | 株式会社イノアックコーポレーション | Sealing material and manufacturing method thereof |
| PL3677610T3 (en) * | 2019-01-07 | 2022-01-31 | Evonik Operations Gmbh | Preparation of polyurethane foam |
| CN116218202A (en) * | 2023-02-03 | 2023-06-06 | 广东安拓普聚合物科技有限公司 | Sealing ring material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA999400A (en) * | 1972-04-28 | 1976-11-02 | General Tire And Rubber Company (The) | Flame retardant flexible polyurethane foams |
| JPS60139445A (en) * | 1983-12-27 | 1985-07-24 | 株式会社イノアックコーポレーション | Flame-retardant polyurethane foam for flame lamination |
| US4876291A (en) * | 1988-08-24 | 1989-10-24 | J.M. Huber Corporation | Mineral filler fire retardant composition and method |
| DE3902238A1 (en) * | 1989-01-26 | 1990-08-02 | Jones Parker & Co Ltd | Foamable potting compound with adjustable, preferably longer processing time |
| JPH06279673A (en) * | 1993-01-07 | 1994-10-04 | Bayer Ag | Nonhalogenous flame-retardant polyamide molding material |
| EP0791613B1 (en) * | 1996-02-14 | 1999-04-14 | Sika AG, vorm. Kaspar Winkler & Co. | Flame-retardant polyurethane systems |
| JPH09249728A (en) * | 1996-03-19 | 1997-09-22 | Inoac Corp | Flame-retardant polyurethane foam |
| JPH11140150A (en) * | 1997-11-13 | 1999-05-25 | Chisso Corp | Composition for low-smoking flame-retardant polyisocyanurate foam and low-smoking flame-retardantfoam prepared therefrom |
| JPH11291375A (en) * | 1998-04-10 | 1999-10-26 | Achilles Corp | Fixed form elastic foamed sealing material and manufacture thereof |
| DE19921472A1 (en) * | 1999-05-08 | 2000-11-16 | Sued Chemie Ag | Flame retardant polymer composition |
| JP2002226545A (en) | 2001-01-31 | 2002-08-14 | Sanyo Chem Ind Ltd | Polymer polyol composition and method for producing polyurethane resin |
| JP2003221425A (en) | 2002-01-31 | 2003-08-05 | Sanyo Chem Ind Ltd | Method for producing polyurethane foam |
-
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- 2004-12-09 CN CNB2004101003111A patent/CN100393805C/en active Active
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| JP4544853B2 (en) | 2010-09-15 |
| KR101133148B1 (en) | 2012-04-06 |
| CN100393805C (en) | 2008-06-11 |
| JP2005171102A (en) | 2005-06-30 |
| TW200519163A (en) | 2005-06-16 |
| HK1074456A1 (en) | 2005-11-11 |
| KR20050058220A (en) | 2005-06-16 |
| CN1637108A (en) | 2005-07-13 |
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